Azo-dyestuffs and process of making same



Patented Jan. 10,1950

UNITED STATES PATENT OFFICE 2,494,416 AZO-DYESTUFFS AND PROCESS OF MAKING SAME Fritz Straub, Kaiseraugst, Walther Hanhart, Riehen, and Emil Mannh assignors to Ciba Lim art, Basel, Switzerland, ited, a Swiss firm No Drawing. Application April 3, 1945, Serial No.

586,436. In Switzerland March 28, 1944 Section 1, Public Law .690, August 8, 1946' Patent expires March 28, 1964 15 Claims. (Cl. 260-460) It is well known in azo chemistry that there are many azo dyestuffs 'of comparatively poor fastness to light. It is further known that azo dyestufls containing in both radicals, interconnected by an azo' group, a so-calledlake-forming' is not capable of forming complex metal compounds or at least no stable complex metal compounds are formed.

The present invention is concerned with dyestuffs derived from diazo compounds containing a sulfonic acid grouping or its equivalents in ortho position to the diazo group. More particularly the present invention provides new substantive dyestuffs derived from pyrazolones as coupling components which contain lake-forming groups. Due to the presence of the said lake-forming groups the resulting dyestufis are capable of forming stable complex metal compounds. It is surprising to see that in such azo dyestufis (as hereinafter defined) the sulfonic acid grouping in ortho position to the azo group brings about a substantially increased fastness to light although, as explained above, the ortho-sulfo-ortho-hydroxy azo grouping is not capable of forming stable complex metal compounds.

stuffs are obtained by coupling diazo compoundsof amines of substantive character which in ortho-position to at least one diazo-group contain a sulfonic acid group or sulfonamide group, with pyrazolones having lake-forming groups and, if desired, bytreating the resulting dyestufi's with agents yielding metal.

The amines of substantive character used in the present process as diazo components may either be used directly as such or may be formed only in the course of the preparation of the dyestuff, i. e. wholly or partly after the coupling with the corresponding pyrazolones. For thepurpose of this invention amines of substantive character are amines which, if coupled with indiiferent azocomponents, such as 2-hydroxy-naphthalene, are capable of producing substantive dyestuffs. Such amines may belong to the benzene or naphthalene S0311 scan NH-O O-NH ENGNH-C 0O (JO-NH NH, O! 0! 01' C0NH N=N -NH--C 0- N N \O/ som soar HiN NH-C o-NHOONH,

C-NH 80311 N/ \N sou:

I Jammie ME NH.

SOQNH, some,

H:N NH-C 0-NH NHi According to this invention valuable azo-dyeandalso the corresponding mixed ureas.

It is to ibe unders'tood that the above amines or diam'ines may contain various substituents normally occurring in substantive azo-dyestuffs, such as halogen atoms (especially chlorine and bromine), nitro groups, alkyl and alkoxy groups,- such as methyl, methoxy, ethoxy, propyloxy, iso- Inithe case of triazine propyloxy groups, etc. compounds only one or threeicorh podnds containing a diazotizable amino group may beatta' ched to the triazine ring, or the aniline radicalzshown in the above formula may be replacedzby the radical of other amines such as methyL ethylor ethanol amine. 1

The amines used in the present process as diazo components must not only be of substantive character, but it is necessary-that they contain a sulfonic acid group or 'a sulio'nan'iide group inprtho position to at least one -diazotiza ble amino-group. Equivalents of the sulfonic' acidgroup are :groups which are readily converted-into sucha group =like sulfonic acid ester grtmps. Sulfonamide groups may contain subs'tituen'tsof various kind, linked to the nitrogen atom in known manner. In :case the amine contains more than one, for example two or 'more :d'iazotizable amino groups, :sulfonic acid groups or sulfonamid'e groups ma be linked in ortho-position to more than one, preferably to two or, if more are present, even all amino groups. According to the present :process, amines of the :kind :described above, after suitable ,diazotizing (or :tetrazotizing, etc.) are coupled with pyrazolones containing lake-forming. groups. In these ,pyrazolones .the .lake-iorming groups may, for instance, vbe linked to a radical acting as substituent of the pyrazolone ring, for ex ample .a naphthalene radical or especially a phenyl radical. Lake forming ;groups may be attachedras wellto some otherradical which is connected with the pyrazolone through various bridge members, for instance again to a phenyl radical. 'l'ake lorming groups there may be used the generally known groups of this kind, more especially, however, the 'salicyclic acid grouping. Bridge members, if present, -.may be of *s'ubstantivating character, :like :the am group in para-position, the benzidine grouping and the .carbonamide grouping.

The following are examples of such pyrazclones which, besides, may be substituted in known manner, for instance in "3 -'position by a methyl or carboxyl group: l- (3'-carboxy-4-hy droxyphenyl) 3 methyl-S pyraZolone and 1-- phenyl 3 methyl-5-pyrazolone-4'-carboxy1ic acid-4 -lrydroxy-3 -carboXy-'1'f anilide.

Coupling of the diam-compounds with the pyrazolones can be effected in known mannerin an alkaline medium, for example, in a medium alkaline with alkali-carbonate.

Instead of coupling the finished substantive diazo compound with the pyrazolories,. it is in many cases quite as easy or even moreexpedient to build up the radical of the diazo component,

which determines the afiinity for the vegetable fiber, wholly or partly only after coupling with the pyrazolones. In such cases, "a simple amine of the benzene :or naphthalene series for instance, which contains in ,ortho-position to the amino group a sulfonic'acid or sulfonamide-group, and, as further substituent, for .instance in para-position to the amino-group, a group which is suitable for a linking-reaction, for example one 4 whereupon, .in subsequent steps, the linking-reactions can take 'place, "for instance the conversion of the substituent referred to into an amino group and the change of the amino group f into a suitable bridge member, such as an acid amide group, a urea group, an azo group, etc.

Similarly, an :a'c'id :group, for instance a carboxyl nitrogen groups contained group containedfin the original amine may be condensed with further amines to build up afterwards :the radical of a substantive amine in this way. It is also possible to link by reduction any in the original mnines, for instance by the action of weak rewhich is readily transformed into an an'iino---- group, can be diazotized and coupled with pyrazolone's'" 'mavmg alake' forming group,

duci-ng agents, like dextrose, in an alkaline medium, whereby azoor azoxy groups are formed. Such methods .of working being generally .known, they need not be explained in detail here.

The iazoqdyestufis obtained according to present process :contain at least one, though preferably two or more rasp-groups. Thanksrtotheir substantive character they are used "above all for dyeing and printing cellulosic fibers, such as cotton, linen, rayon :and staple :fiber :from regenerated cellulose and, -.under certain weir cumstances, also for edyeing :an'ima-l fiber-s, such as wool gar :leather.

Specially valuable rmsults are obtained :if the dyestufis are treated with agents yielding metal, either in substance, in the dyebath or on the fiber. Suitable in this connection are agents yielding, for instance, iron, chromium, and especially copper; "in certain cases several agents yielding metal may be "used simultaneously, for

1 example mixtures of agents yielding chromium and copper.

Depending upon thechoice of components used for the construction of the dyes'tuif and especially upon the number of the water-solubiliz'inggroups contained therein, especially .sulfonic acidand carboxyl groups, itmay be appropriate .to convert the dyestus .into the @complex metal .compounds in substance, .in .the idyeba-th, .or even only .on the .fiber, the latter procedure .being preferable if the water-solubility of the dyestuffs prepared in substance would be 'insnflicient. In ithis .CQSG it is of advantageto apply the dyeing process of U. PatentlNo. ,2,-l48,;659.,according to which the .same bath :is first used for dyeing (and afterwards for the treatment with agents yielding metal. Agents :yielding 3111811821 that .are resistant to alkaline solutions, like complex copper tartrates and others, are especially suitable in this In all other respects the treatment with agents yielding metal may be performed in known manner.

The present process permits, among other things, the production of dyestuffs dyeing fast yellow, orange, and yellow-brown shades, especially noted for their fastness to light.

--The'=following examples illustrate the inven- 'tion, the parts being -by weight:

Example 1 v21.8 parts of i-nitro-l-aminobenzene-Z-sulrfonic acid are diazotized in known manner and coupled with 23.4 parts of l-( l'-hydroxy-3'-carboxyphenyD-eli-methyl-5-pyrazolone in a solution alkaline with sodium carbonate. After the cou plirrgiisgcomplte, 483parts of crystallized sodium sulfide are added, the whole is heated for some time 50 55 62., neutralized with-dilute hydro- 5...?- chloric acid and the dyestuff is precipitated by the-addition of sodium chloride. The aminoazo dyestuff is filtered off, dissolved in 1500 parts of water and, after the addition of parts of crysarts to 60 C. for half an-hour. 300 parts-of sodium chloride are then added and the dyestufl; is filtered after cooling. The dried dyestufl of the formula no s 5 OH I I 80111 cm rivd-on or no-i i. N N- tallized sodium acetate and parts of I parais a'i-bijownpowder dissolving with abrown-yellow n roen oylride, is stirred while, b ng colo ation in water or concentrated sulfuric acid heated until it is impossible to detect an amino 1 b and dyeing-cotton'in' the presence of copper salts compound. The nitro-benzoylated dyestufi-i is in-fast'bro'wn-yellow shades. 3 separated by the addition of some sodium ch10 Exam l6 3 ride and filtered off, then dissolved in 2000 parts p Iv of water and some sodium carbonate, to'make'the U 55.4; partsof 41 a 0- D y -u solution about neutral, then stirred for several 3':3"-disu'lfonic acid of the formula hours at 60-65 C. after addition o f-48'vlpartsjof it 1L0]; ..\N/ v E is a brown powder, dissolving with a yellow coloration in water or concentrated'sulf-uric acid and M dyeing cotton in the presence of "copper salts Moi-O0 O--NH whichis' p re exactly like that xample i,

is dissolvedin 2000 parts of warm water and, after additionoi 185 parts of caustic" soda solution of percent. strength and 240 parts of an aqueous After filtering ofi NHC oONn-oo-NnOoo-mi- N=N- -2 v p HO N are dissolvedin 800 parts of hot water with the addition of sodium carbonate to obtain about a neutral reaction,-poured into a thoroughly stirred mixture of 80 parts of hydrochloric acidof 30 per cent. strength and ice water after addition of 14 parts of sodiumhitrite-and then stirred for severalhour's'. The whole is then mixed with a soluaj ti'oii alkaline withsodium carbonate of' 47 parts brown powder, dissolving with a brown-orange coloration in water or concentrated sulfuric acid and dyeing cotton in the presence of copper salts in fast brown-yellow shades.

- The same dyestufimay be obtained by coupling diazotized '4-a'cetylamino 4 aminodi-i phenyl'- 3'-sulionic acid with the above pyrazolone,

splitting off the acetyl group and subsequently treating with phosgene.

E q mmple 4 69.2 parts of the condensation product from 2 dextrose solution of 10 per cent.strength, is stirred mols of 4:4-diaminodiphenyl-3-sulfonic acid,

z. onennolaof' aniline; and: 1 mol of: cyanunic chl'lifl de otstheyf mula i Y are dissolved as sodium salt in 1000 parts of hot water and, after addition of 14 parts of sodium nitrite, poured. into a thoroughly stirred mixture of 80; parts of hydrochloric acid 'of 13p per cent, strengthand ice water. After stirring, ion-some time while cooling the resulting, tetrazo. cem= pound is coupled with a solution alkaline with sodium carbonate of'flparts of 1-(4'-hydroxy- 3L carboxyphenyh -3-methyl'-5+pyrazolone. when coupling is complete the precipitatedldyestuffa is filtered off and dried. It is a brown powder dissolving with a brown-orange coloration in water m e I 215x311 red-brown powder dissolving; in water with am erange-yeliow, and in concentrated; sulturia acid with a, yellow coloration and dyeing cotton in the presence of copper salts in orange-yellow shades iastto light.v

snip-pants: of 4.;4! diaminodiphenyl-3g3' -di-s sul'ionic'acid are tetrazotized in theusualzma n-nner'arid' then coupled: in a solution alkaline: with sodium: carbonate with 4.6.8 parts of 1-(4! -hy 25 droxy 3 carboxyphenol): 3.:-met'hyl;-.- 5'- pyra-zolone, When coupling is complete, the dyestuff of the formula Shani or concentrated sulfuric acid and dyeing; cotton in. the presence, of copper salts brown-yellow shadesfast to light. v, i

A very similar dyestufi'is obtained by first preparing the aminoazo-dyestufi" and condensing it with cyanuric chloride. Example 5 21.7 parts of 1-amino-4-nitrobenzene-2-sulfamide are diazotizecl in known manner, then coupled in an alkaline solution with 36 parts of the pyrazolone of the formula COOH "H and when coupling is complete, "are into" the aminoazo dyestuff 'by' heating-"with '48 parts of crystallized sodium sulfide-for memhours;. The d'yestuif isprecipitated by thezadditi'onzof sodium chloride; then filtmzedi and'- cnm-- vcntecr into the. urea in knownrmannen ment with phosgene. The dry dyestuff of the formula is precipitated by the additionof sodium chloride, filtered oil and dried; It is a red-brown powder, dissolving in water with a ye1l w-b rown 40 in concentrated sulfuric acid with yellow-red coloration and dyeing cotton in the presence of copper salts in red-brown shades very fast to light. l .t

A similardyestufi' is obtained by the use at sultonic acid instead of the 4:4-diaminodi phenyl-3:3-disulfonic acid.

Example 7 50 34.4 parts of 4:4'-diaminodipheny1-3-:3'-dlsulfonic acid are tetrazotized in the usual manner and then coupled in a solution alkaline'with sodium carbonate with 70.6 parts of the. pyracos lone ofy1the formula 11 on o coon 60 Some sodium chloride is added after the coupling cornfplete and the dyestuff is filtered. 011 and dried. -';It is a red-brown powder, dissolvinglwith orange-brown coloration in water and concentratedsulfuric acid and dyeing cotton in the 9 10 presence of copper salts in fast brown-yellow with =:the same coupling component andsu bs shades. que'ntly converted in usual manner into the para:

Example 8 amincbenzoylaminorcompound, and represented. b th formula V. 33.7 parts of 4-amino-4'-hydroxy-3-carboxy- 5 1 I 803E 1:1'-azobenzene-3-sulfonic acid are diazotized in t the usual manner and coupled in a solution alka- HEN OOTNH N C line with sodium carbonate with 35.3 parts of the l I v w HO N pyrazolone of the formula v on, N

' 7 COOH When coupling is complete, the dyestufi is pro-- cipitated by the addition of sodium chloride, fil- H tered off and dried. It corresponds to the forare dissolved in 1000 parts of water with the addimula tion of sodium carbonate and at a temperature of C=N OOH 6 and is dark brown powder dissolving in water to 50 0. treated with phosgene until it is no with brownish-yellow, and in concentrated sul-' longer possible to detect yan amino compound; furic acid with red coloration and dyeing cotton brilliant yellow paper should always indicate a in the presence of copper salts in fast brownslightly alkaline reaction." 'The'-dyestufi which red shades. may" containminor proportions of symmetrical mmp 9 30 compounds, but chiefly consists of the compound 5.1 parts of the dyestufl obtained from diazoof the formula I I s03H j 'SOiH CH3 I I Y Ha' 1% 0-013. 1 v HOO it .QQQH v v V U Q 7 H000 H "I: '7': I. H .Q' tized 4-amino-4-acetylamino-diphenyl-3-sulis completely precipitated loy sodium chloride,

fonic acid and 1- (4'-hydroxy-3'-canboxyphenyl) filtered and dried. It is a red-brown powder dis- 3-methyl-5-zpyrazolone and saponified with dilute in i n ntr ted sulfuric acid with a caustic soda solution, and represented by the n-ye w, in Water-with yellow-brown colorf l ation and dyeing cotton in the presence of copper salts in fast yellow-brown shades. s ousr Example 10 4.3 parts of the dyestuff obtained from diazo- 7 mN-OQN=N -c-om tized 4-nitro-l-aminobenzene-Z-sulfonic acid and i o pyrazolone and reduced torthe aminoazo-dyestuif 1 by means ofyisodiumsulfide and 5,5parts of; the

para-amnobenzoyleamino azoedyestufi obtained;

ibytreating the dyestufi described above with 000K m re in 1 0Q P r s-of wat r wi h dd of sonata-mi i en y c loride d. r cin e is-.

H 1 ca bon e and-trea d withp seeneata temperature of 40 to 50 C. until it is no longer possible to detect an amino compound. The dyeand 5.5 parts of the dyestuff obtained from distuff thus obtained and chiefly corresponding to azotlzed 4-m'tro-1-aminobenzene-2-sulfonic acid the iormula soa SOaH v H: ent ngleG NH C;O NHGN=N C l 'r "JLOH' Ho-tt it N Q coon (I 1 nooc is precipitatedby the :additionrofrsodium chloride, fiitered on and dried. is a med-brown powder, dissoiiiing concentrated sulfuric acid and 'in water with a yellow-lbrown coloration and dyein cotton in the presence of copper salts in fast brown-yellow shades.

As'imilar dyestufl? is obtained ifthefiirst-named aminoazo-dyestufl is replaced by that of the formula .100 pantsof cotton are introduced at a tempera-V ture of 40 C. intoa dyebath containing 1 part of the dyestulfi .obtainedgaccording to paragraph .l of Example 1 as well as 2 parts or anhydrous sodium carbonate in 3000 parts of water, the whdle is heated to 90 C. and 30 parts of crystallized sodium sulfate are added. .Dyeingis carried on at 90 to 100 C. during 45 minutes and-the loath 'is then cooled to 70 C., and a neutralized solution of 1 part Of complex copper tartrate is added beiore dyeing is resumed for another 30 minutes at a temperature of '70 to 80 C. The cotton is then rinsed and, if desired, soaped. It is dyed in fast yellow tints.

What we claim is:

1. :An azo-dyestufi oi the formula wherein "each axis a substituentstanding in orthoposition to the corresponding azo-group selected from the group consisting of sulionic acid and sulfon'amide groupings, -.t- R- x stands for the radical of a diainine or substantive character for cellulo'sic fibers, and wherein each R1 stands -ior the radical of an aromatic compound containing up to two benzene nuclei and a salicylic acid grouping.

s COOK 12 2. .An-azo-dyestufl gr the formula wherein each a: is a substituent standing orthoposition to'the corresponding azo-grcup selected from the group consisting of sulfonic acid and sulfonaniide groupings, :r-R-:r stands for the radical of a 'diamine of substantive character for cellulosic fibers and containing at least one diphenyl grouping, and wherein each R1 stands for the radical of an aromatic compound containing up to two benzene nuclei and a salicylic acid grouping.

wherein each a is -a substituent standing in orthoposition to the corresponding azo-group selected from the group consisting of sulfonic acid and sul fonamide groupings, :r-R-x stands for the radical of a diamine of substantive character for cellulose fibers and containing at least one diphenyl grouping and a urea grouping, and wherein each R1 stands for the radical of an aromatic compound containing up to two benzene nuclei and a salicylic acid grouping.

1 6.. The dyestufl' of the formula; r

7. The dyestuff of the formula 8. Process for the manufacture of an azo-dyestuff, comprising coupling a tetrazo compound of a diamine of substantivecharacter, for cellulosic fibers and carrying in ortho position to at least one diazo group a substituent selected irom the group consisting of sulfonic acid and sulfoiiamide groupings, with salicylic acid grouping.

v pyrazolone containing a 9. Process for the manufacture of an azo-dyestufi, comprising coupling a tetrazo compound of a diamine of substantive character for cellulosic fibers and carrying in ortho-position to both diazo groups a substituent selected from the group consisting of sulfonic acid and sulfonamide groupings, with pyrazolone containing a salicylic acid grouping.

COOH

position to the azo-group selected from the group consisting of sulfonic acid and sulfonamide groupings, Pz stands for the radical of a pyrazolone coupling. component containing a salicylic acid grouping, R2 stands for the radical of an aromatic compound containing up to two benzene nuclei in which the groups N=N and NI- Iz' and the linkage of the benzene nuclei stand} in para-position to each other, with cyanuric chlorideunder conditions known to be suitable I for attaching the said amino azo-dyestuifs to the triazine ring with elimination of hydrogen chloride.

l2 Process for the manufacture of an azo-dye- 'stufi; comprising coupling the tetrazotized diamineof the formula 10. Process for the manufacture of an azo-dyestufl, comprising reacting an amino azo-dyestufi of the formula wherein a: is a substituent standing in orthoposition to the azo-group selected from the group consisting of sulfonic acid and sulfonamide groupings, Pz stands for the radical of a pyrazolone coupling component containing a salicylic acid grouping, R2 stands for the radical of an arcmatic compound containing up to two benzene nuclei in which the groups -N=N and NH: and the linkage of the benzene nuclei stand in para-position to each other, with phosgene under conditions known to be suitable for the formation of a urea bond.

11. Process for the manufacture or an azo-dyestufi, comprising reacting an amino azo-dyestufl or the formula wherein a: is a substituent standing in ortho- I with two molecular proportions of 1-(4'-hydroxy- 3'-carboxy-phenyl-) 3-methyl-5-pyrazolone.

13. Process for the manufacture of an azo-dyestuiI, comprising reacting one molecular proportion of the amino azo-dyestufl. of the formula COOH and one molecular proportion of the aminoazodyestufl of the formula Certificate of Correction Patent No. 2,494,416 January 10, 1950 FRITZ STRAUB ET AL.

It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows:

Column 4, line 43, for dyestus read dyestufi's; column 8, line 25, for carboxyphenol) read carbowyphenyl); column 9, last formula in Example 8, for

column 13, lines 31 and 39, before pyrazolone insert a;

and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 9th day of May, A. D. 1950.

THOMAS F. MURPHY,

Assistant flommissz'oner of Patents. 

1. AN AZO-DYESTUFF OF THE FORMULA 